Synthesis and structure of triphenylbismuth difluoride

Article abstract of DOI:10.1023/A:1015328925333

The reaction of triphenylbismuth dichloride with sodium fluoride in acetone leads to formation of triphenylbismuth difluoride in 73% yield. The X-ray diffraction data show that the bismuth atom in the two symmetrically independent molecules of bismuth dif

Full text of DOI:10.1023/A:1015328925333

Russian Journal of General Chemistry, Vol. 72, No. 1, 2002, pp. 44 45. Translated from Zhurnal Obshchei Khimii, Vol. 72, No. 1, 2002,
pp. 49 50.
Original Russian Text Copyright
2002 by Sharutin, Sharutina, Egorova, Ivanenko, Bel’skii.
Synthesis and Structure of Triphenylbismuth Difluoride
V. V. Sharutin, O. K. Sharutina, I. V. Egorova, T. K. Ivanenko, and V. K. Bel’skii
Blagoveshchensk State Pedagogical University, Blagoveshchensk, Russia
Received July 18, 2000
Abstract The reaction of triphenylbismuth dichloride with sodium fluoride in acetone leads to formation
of triphenylbismuth difluoride in 73% yield. The X-ray diffraction data show that the bismuth atom in the two
symmetrically independent molecules of bismuth difluoride has a trigonal-bipyramidal coordination with
equatorial fluorine atoms. The Bi F and Bi C distances are 2.53(1) 2.59(1) and 2.10(3) 2.22(2) , respec-
tively, and the FBiF angle is 175.1(5) .
It is known that the triphenylbismuth difluoride
prepared from triphenylbismuth dibromide and potas-
sium fluoride melts at 127.5 C. At the same time, the
reaction of triphenylbismuth dihalide with silver
fluoride in benzene evidently leads to another crystal
modification which melts at 158.5 159 C [2]. We
slightly changed the conditions of synthesis of tri-
phenylbismuth difluoride I melting at 127.5 C (reac-
tion of sodium fluoride and triphenylbismuth di-
chloride in aqueous acetone) and studied its crystal
structure.
EXPERIMENTAL
X-ray diffraction analysis of crystals of tri-
phenylbismuth difluoride (I). The unit cell para-
meters and the intensities of 1116 unique reflections
with I > 2 (I) were measured on an Enraf Nonius
CAD-4 automatic diffractometer ( MoK radiation,
0.71073 , Nb filter, 2 / scanning). The crystals
are orthorhombic; at 20 C, a 9.140(2)
, b
17.122(3) , c 22.339(4); V 3496(1) 3; space group
P212121, Z 8, dcalc 1.817 g/cm3. The structure was
solved by the heavy atom method and refined aniso-
tropically for non-hydrogen atoms and isotropically
for hydrogen atoms to R 0.0386 and RW 0.1104. All
the calculations were carried out using the SHELXL-
97 program package [4].
The X-ray diffraction data show that the bismuth
atom in the two symmetrically independent molecules
of compound I has a distorted trigonal-bipyramidal
coordination with axial fluorine atoms. The angles
between equatorial phenyl substituents are slightly
different [113.6(10) , 118.5(12) , and 127.9(12) in
molecule A and 118.2(11) , 120.5(9) , and 121.3(11)
in molecule B], but axial FBiF angles are practically
equal to each other [175.1(5) and 175.6(5) ]. Note
that in the molecule of triphenylbismuth bis(trifluoro-
acetate) in which the bismuth atom has the coordina-
tion number 7 the respective angles are 110.1(3) ,
109.2(3) , and 140.6(3) [3].
Triphenylbismuth difluoride (I). To a soilution
C11
C12
C10
C9
F2
C5
C3
C8
C6
C2
C7
C1
Bi1
C4
The bismuth atom in molecule A lies practically
in the equatorial plane (the deviation from the plane
is 0.001 ), while in molecule B this deviation is
larger (0.017 ). Both in A and in B, different torsion
angles of phenyl rings with respect to the equatorial
plane are observed: 72.9 , 67.2 , and 31.6 in A and
115.7 , 35.7 , and 103.5 in B. The spatial arrange-
ment of molecule A of compound I is presented in the
figure. The atomic coordinates are listed in Table 1,
and the bond lengths and bond angles, in Table 2.
C18
C13
F1
C17
C16
C14
C15
Overall view of molecule A of compound I.
1070-3632/02/7201-0044$27.00 2002 MAIK Nauka/Interperiodica

SYNTHESIS AND STRUCTURE OF TRIPHENYLBISMUTH DIFLUORIDE
45
Table 1. Atomic coordinates ( 104, ) and equivalent
isotropic thermal parameters (B 103, 2) in the molecule
of triphenylbismuth difluoride
Table 2. Bond lengths (d) and bond angles ( ) in the
molecule of triphenylbismuth difluoride
Molecule A
Molecule B
bond
Atom
x
y
z
B
bond
d,
d,
Bi1
Bi2
F1
5885(2)
6477(2)
4578(1)
2253(1)
3321(6)
5779(7)
3365(8)
1095(7)
4240(20)
3710(20)
3475(18)
3780(20)
4314(18)
4546(16)
5344(15)
5060(13)
5538(18)
6299(16)
6582(12)
6105(16)
4244(16)
3523(14)
4856(1)
8026(1)
4320(5)
5363(6)
8619(7)
7410(6)
69(1)
71(1)
15(3)
36(4)
46(5)
25(4)
140(20)
132(18)
210(30)
140(19)
119(17)
120(16)
69(11)
107(15)
150(20)
107(15)
120(16)
114(16)
81(13)
Bi1 C1
Bi1 C7
Bi1 C13
Bi1 F2
Bi1 F1
C1 C2
2.10(3)
2.16(2)
2.22(2)
2.55(1)
2.59(1)
1.39(1)
Bi2 C31
Bi2 C25
Bi2 C19
Bi2 F3
Bi2 F4
C35 C36
2.16(2)
2.21(2)
2.21(2)
2.53(1)
2.55(1)
1.39(1)
4995(15)
6985(17)
5371(17)
7394(15)
4780(40)
3640(50)
2880(40)
3260(40)
4400(40)
5160(30)
4780(30)
4370(30)
3610(40)
3260(30)
3670(40)
4430(30)
8120(20)
8700(30)
F2
F3
F4
C1
5640(11)
5594(14)
6100(20)
6659(15)
6705(11)
6196(15)
4233(12)
3674(13)
3277(10)
3440(13)
3999(14)
4395(11)
4568(12)
4732(12)
4567(13)
4237(13)
4073(11)
4239(11)
8839(11)
9287(16)
9771(13)
9807(12)
9359(14)
8875(11)
7801(13)
8240(10)
8077(14)
7476(16)
7037(11)
7200(11)
7426(14)
6873(16)
6505(12)
6691(16)
7244(17)
7612(12)
C2
C3
C4
C5
angle
, deg
angle
, deg
C6
C7
C1Bi1C7
C13Bi1C1
C7Bi1C13
C1Bi1F2
C7Bi1F2
C13Bi1F2
C1Bi1F1
C7Bi1F1
C13Bi1F1
F2Bi1F1
118.5(1)
127.9(1)
113.6(1)
92.3(1)
89.0(8)
88.5(8)
90.4(1)
93.4(8)
86.6(7)
175.1(5)
C31Bi2C25
C31Bi2C19
C25Bi2C19
C31Bi2F3
C25Bi2F3
C19Bi2F3
C25Bi2F4
C19Bi2F4
F3Bi2F4
118.2(1)
121.3(1)
129.5(9)
91.5(1)
88.4(8)
90.6(9)
87.2(8)
91.5(8)
175.6(5)
C8
C9
C10
C11
C12
C13
C14
C15
C16
C17
C18
C19
C20
C21
C22
C23
C24
C25
C26
C27
C28
C29
C30
C31
C32
C33
C34
C35
C36
107(15)
134(19)
105(14)
108(15)
88(12)
10110(30) 3324(12)
10960(20) 3845(17)
10380(30) 4566(15)
8960(30)
7580(20)
8010(40)
8820(40)
9210(40)
8790(40)
7970(30)
4240(30)
3180(40)
1750(30)
1370(30)
2430(40)
3870(30)
7560(30)
8130(40)
8760(40)
8830(40)
8250(40)
7620(40)
4765(12)
1810(17)
2326(13)
2059(19)
1280(20)
760(14)
1027(15)
1869(14)
1761(16)
1587(15)
1523(15)
1632(18)
1805(17)
3060(16)
2847(15)
3410(20)
4180(20)
4395(14)
3834(19)
63(11)
150(20)
170(20)
150(20)
112(16)
92(13)
Yield 2.08 g, mp 127.5 C. Found,%: C 44.54; H 3.02.
C18H15BiF2. Calculated,%: C 45.19; H 3.14.
ACKNOWLEDGMENT
75(12)
93(13)
V.K. Bel’skii is grateful to the Russian Foundation
for Basic Research for financial support (project
no. 00-03-32578).
111(15)
113(15)
160(20)
141(19)
94(16)
150(20)
134(19)
160(20)
170(20)
126(18)
REFERENCES
1. Challenger, F. and Wilkinson, J.F., J. Chem. Soc., 1922,
vol. 121, pp. 91 94.
2. Goel, R.C. and Prasad, H.S., Can. J. Chem., 1970,
vol. 48, pp. 2488 2493.
3. Ferguson, G., Kaither, B., Glidevell, C., and Smith, S.,
J. Organomet. Chem., 1991, vol. 419, no. 2, pp. 283
291.
of 3.04 g of triphenylbismuth dichloride in 20 ml of
acetone, a solution of 0.50 g of sodium fluoride in
20 ml of water was added. The solvent was removed,
and the residue was crystallized from petroleum ether.
4. Sheldrick, G.M., SHELXL-97, Goettingen: Univ. of
Goettingen, 1997.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 72 No. 1 2002